Azeotropic compositions comprising fluorinated compounds for cleaning applications

ABSTRACT

The present invention relates to compositions comprising fluorinated olefins or fluorinated ketones, and at least one alcohol, halocarbon, hydrofluorocarbon, or fluoroether and combinations thereof. In one embodiment, these compositions are azeotropic or azeotrope-like. In another embodiment, these compositions are useful in cleaning applications as a degreasing agent or defluxing agent for removing oils and/or other residues from a surface.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application is a divisional of pending U.S. application Ser. No. 12/576,273, filed Oct. 9, 2009, which is a division of U.S. application Ser. No. 12/355,879, filed Jan. 19, 2009, now U.S. Pat. No. 7,622,053, which is a division of U.S. application Ser. No. 11/712,453, filed Feb. 28, 2007, now U.S. Pat. No. 7,494,603, which claims the benefit of priority of U.S. Provisional Application 60/777,350, filed Feb. 28, 2006.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compositions comprising fluorinated olefins, or fluorinated ketones, and at least one alcohol, halocarbon, fluoroalkyl ether, or hydrofluorocarbon and combinations thereof. These compositions are azeotropic or azeotrope-like and are useful in cleaning applications as a defluxing agent and for removing oils or residues from a surface.

2. Description of Related Art

Flux residues are always present on microelectronics components assembled using rosin flux. As modern electronic circuit boards evolve toward increased circuit and component densities, thorough board cleaning after soldering becomes a critical processing step. After soldering, the flux-residues are often removed with an organic solvent. De-fluxing solvents should be non-flammable, have low toxicity and have high solvency power, so that the flux and flux-residues can be removed without damaging the substrate being cleaned. Further, other types of residue, such as oils and greases, must be effectively removed from these devices for optimal performance in use.

Alternative, non-ozone depleting solvents have become available since the elimination of nearly all previous CFCs and HCFCs as a result of the Montreal Protocol. While boiling point, flammability and solvent power characteristics can often be adjusted by preparing solvent mixtures, these mixtures are often unsatisfactory because they fractionate to an undesirable degree during use. Such solvent mixtures also fractionate during solvent distillation, which makes it virtually impossible to recover a solvent mixture of the original composition.

Azeotropic solvent mixtures may possess the properties needed for these de-fluxing, de-greasing applications and other cleaning agent needs. Azeotropic mixtures exhibit either a maximum or a minimum boiling point and do not fractionate on boiling. The inherent invariance of composition under boiling conditions insures that the ratios of the individual components of the mixture will not change during use and that solvency properties will remain constant as well.

The present invention provides azeotropic and azeotrope-like compositions useful in semiconductor chip and circuit board cleaning, defluxing, and degreasing processes. The present compositions are non-flammable, and as they do not fractionate, will not produce flammable compositions during use. Additionally, the used azeotropic solvent mixtures may be re-distilled and re-used without composition change.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to compositions comprising fluorinated olefins and, at least one compound selected from the group consisting of alcohols, halocarbons, fluoralkyl ethers, and hydrofluorocarbons and combinations thereof. In one embodiment, the at least one compound is selected from the group consisting of:

n-propylbromide;

trichloroethylene;

tetrachloroethylene;

trans-1,2-dichloroethylene;

methanol;

ethanol;

n-propanol;

isopropanol;

C₄F₉OCH₃,

C₄F₉OC₂H₅;

HFC-43-10mee;

HFC-365mfc

and combinations thereof.

In one embodiment, the compositions are azeotropic or azeotrope-like. Additionally, the present invention relates to processes for cleaning surfaces and for removing residue from surfaces, such as integrated circuit devices.

DETAILED DESCRIPTION OF THE INVENTION

Applicants specifically incorporate by reference the entire contents of all cited references in this disclosure. Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

In one embodiment, the present invention relates to compositions comprising compounds having the formula E- or Z—R¹CH═CHR² (Formula I), wherein R¹ and R² are, independently, C1 to C5 perfluoroalkyl groups, and at least one alcohol, halocarbon, fluoroalkyl ethers, or hydrofluorocarbon and combinations thereof. Examples of R¹ and R² groups include, but are not limited to, CF₃, C₂F₅, n-C₃F₇, i-C₃F₇, n-C₄F₉, n-C₅F₁₁, and i-C₄F₉. Exemplary, non-limiting Formula I compounds are presented in Table 1.

TABLE 1 Code Structure IUPAC Name F11E CF₃CH═CHCF₃ 1,1,1,4,4,4-hexafluoro-2-butene F12E CF₃CH═CHC₂F₅ 1,1,1,4,4,5,5,5-octafluoro-2-pentene F13E CF₃CH═CH(n-C₃F₇) 1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene F13iE CF₃CH═CH(i-C₃F₇) 1,1,1,4,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene F22E C₂F₅CH═CHC₂F₅ 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene F14E CF₃CH═CH(n-C₄F₉) 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene F23E C₂F₅CH═CH(n-C₃F₇) 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene F23iE C₂F₅CH═CH(i-C₃F₇) 1,1,1,2,2,5,6,6,6-nonafluoro-5- (trifluoromethyl)hex-3-ene F15E CF₃CH═CH(n-C₅F₁₁) 1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetraddecafluorooct- 2-ene F24E C₂F₅CH═CH(n-C₄F₉) 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct- 3-ene F3i3iE i-C₃F₇CH═CH(i-C₃F₇) 1,1,1,2,5,6,6,6-octafluoro-2,5- bis(trimethylfluoro)hex-3-ene F33iE n-C₃F₇CH═CH(i-C₃F₇) 1,1,1,2,5,5,6,6,7,7,7-undecafluoro- 2(trifluoromethyl)hept-3-ene F34E n-C₃F₇CH═CH(n-C₄F₉) 1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9- hexadecafluoronon-4-ene F3i4E i-C₃F₇CH═CH(n-C₄F₉) 1,1,1,2,5,5,6,6,7,7,8,8,8-triskaidecafluoro- 2(trifluoromethyl)oct-3-ene F44E n-C₄F₉CH═CH(n-C₄F₉) 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10- octadecafluorodec-5-ene

Compounds of Formula I may be prepared by contacting a perfluoroalkyl iodide of the formula R¹I with a perfluoroalkyltrihydroolefin of the formula R²CH═CH₂ to form a trihydroiodoperfluoroalkane of the formula R¹CH₂CHIR². This trihydroiodoperfluoroalkane can then be dehydroiodinated to form R¹CH═CHR². Alternatively, the olefin R¹CH═CHR² may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane of the formula R¹CHICH₂R² formed in turn by reacting a perfluoroalkyl iodide of the formula R²I with a perfluoroalkyltrihydroolefin of the formula R¹CH═CH₂.

Said contacting of a perfluoroalkyl iodide with a perfluoroalkyltrihydroolefin may take place in batch mode by combining the reactants in a suitable reaction vessel capable of operating under the autogenous pressure of the reactants and products at reaction temperature. Suitable reaction vessels include those fabricated from stainless steels, in particular of the austenitic type, and the well-known high nickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickel based alloys and Inconel® nickel-chromium alloys. Alternatively, the reaction may take be conducted in semi-batch mode in which the perfluoroalkyltrihydroolefin reactant is added to the perfluoroalkyl iodide reactant by means of a suitable addition apparatus such as a pump at the reaction temperature.

The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefin should be between about 1:1 to about 4:1, preferably from about 1.5:1 to 2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1 adduct as reported by Jeanneaux, et. al. in Journal of Fluorine Chemistry, Vol. 4, pages 261-270 (1974).

Temperatures for contacting of said perfluoroalkyl iodide with said perfluoroalkyltrihydroolefin are preferably within the range of about 150° C. to 300° C., more preferably from about 170° C. to about 250° C., and most preferably from about 180° C. to about 230° C. Pressures for contacting of said perfluoroalkyl iodide with said perfluoroalkyltrihydroolefin are preferably the autogenous pressure of the reactants at the reaction temperature.

Suitable contact times for the reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18 hours, preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkane prepared by reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be used directly in the dehydroiodination step or may preferably be recovered and purified by distillation prior to the dehydroiodination step.

In yet another embodiment, the contacting of a perfluoroalkyliodide with a perfluoroalkyltrihydroolefin takes place in the presence of a catalyst. In one embodiment, a suitable catalyst is a Group VIII transition metal complex. Representative Group VIII transition metal complexes include, without limitation, zero valent NiL₄ complexes, wherein the ligand, L, can be a phosphine ligand, a phosphite ligand, a carbonyl ligand, an isonitrile ligand, an alkene ligand, or a combination thereof. In one such embodiment, the Ni(0)L₄ complex is a NiL₂(CO)₂ complex. In one particular embodiment, the Group VIII transition metal complex is bis(triphenyl phospine)nickel(0) dicarbonyl. In one embodiment, the ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefin is between about 3:1 to about 8:1. In one embodiment, the temperature for contacting of said perfluoroalkyl iodide with said perfluoroalkyltrihydroolefin in the presence of a catalyst, is within the range of about 80° C. to about 130° C. In another embodiment, the temperature is from about 90° C. to about 120° C.

In one embodiment, the contact time for the reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin in the presence of a catalyst is from about 0.5 hour to about 18 hours. In another embodiment, the contact time is from about 4 to about 12 hours.

The dehydroiodination step is carried out by contacting the trihydroiodoperfluoroalkane with a basic substance. Suitable basic substances include alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide), alkali metal oxide (for example, sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or mixtures of basic substances such as soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide.

Said contacting of the trihydroiodoperfluoroalkane with a basic substance may take place in the liquid phase preferably in the presence of a solvent capable of dissolving at least a portion of both reactants. Solvents suitable for the dehydroiodination step include one or more polar organic solvents such as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choice of solvent depends on the solubility of the basic substance, the solubility of the perfluoroalkyl iodide, and the solubility of the perfluoroalkyltrihydroolefin as well as the boiling point of the product, and the ease of separation of traces of the solvent from the product during purification. Typically, ethanol or isopropanol are good solvents for the reaction. Separation of solvent from the product may be effected by distillation, extraction, phase separation, or a combination of the three.

Typically, the dehydroiodination reaction may be carried out by addition of one of the reactants (either the basic substance or the trihydroiodoperfluoroalkane) to the other reactant in a suitable reaction vessel. Said reaction vessel may be fabricated from glass, ceramic, or metal and is preferably agitated with an impellor or other stirring mechanism.

Temperatures suitable for the dehydroiodination reaction are from about 10° C. to about 100° C., preferably from about 20° C. to about 70° C. The dehydroiodination reaction may be carried out at ambient pressure or at reduced or elevated pressure. Of note are dehydroiodination reactions in which the compound of Formula I is distilled out of the reaction vessel as it is formed.

Alternatively, the dehydroiodination reaction may be conducted by contacting an aqueous solution of said basic substance with a solution of the trihydroiodoperfluoroalkane in one or more organic solvents of lower polarity such as an alkane (e.g., hexane, heptane, or octane), aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g., methylene chloride, ethylene dichloride, chloroform, carbon tetrachloride, or perchloroethylene), or ether (e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane, dimethoxyethane, diglyme, or tetraglyme) in the presence of a phase transfer catalyst. Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylylmethylammonium chloride), quaternary phosphonium halides (e.g., triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride), cyclic ether compounds known in the art as crown ethers (e.g., 18-crown-6 and 15-crown-5).

Alternatively, the dehydroiodination reaction may be conducted in the absence of solvent by adding the trihydroiodoperfluoroalkane to one or more solid or liquid basic substance(s).

Suitable reaction times for the dehydroiodination reactions are from about 15 minutes to about six hours or more depending on the solubility of the reactants. Typically the dehydroiodination reaction is rapid and requires about 30 minutes to about three hours for completion.

The compound of formula I may be recovered from the dehydroiodination reaction mixture by phase separation, optionally after addition of water, by distillation, or by a combination thereof.

In another embodiment, the invention relates to compositions comprising perfluoroethyl isopropyl ketone (1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone, (PEIK) and at least two compounds selected from the group consisting of alcohols, halocarbons, fluoralkyl ethers, and hydrofluorocarbons. PEIK has CAS Reg. No. 756-13-8) and is available from 3M™ (St. Paul, Minn.).

In yet another embodiment, the invention relates to compositions comprising nonafluoro-1-hexene (3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene), (PFBE), and at least one compound selected from the group consisting of alcohols, halocarbons, fluoralkyl ethers, and hydrofluorocarbons and combinations thereof. 3,3,4,4,5,5,6,6,6-Nonafluoro-1-hexene, also known as HFC-1549fz, has CAS Registry Number 19430-93-4 and is available from E.I. DuPont de Nemours & Co (Wilmington, Del.).

In yet another embodiment, the invention relates to a process for cleaning surfaces using azeotropic or azeotrope-like compositions comprising a fluorinated olefin, or a fluorinated ketone and at least least one compound selected from the group consisting of alcohols, halocarbons, fluoroalkyl ethers, and hydrofluorocarbons.

The fluorolefins of Table 1, PEIK, and PFBE may be combined with the compounds listed in Table 2 to form the present inventive compositions. The at least one compound selected from the group consisting of alcohols, halocarbons, fluoroalkyl ethers, or hydrofluorocarbons to be combined with PFBE shall not be an alcohol, trans-1,2-dichloroethylene alone, C₄F₉OCH₃ alone, HFC-43-10mee alone, HFC-365mfc alone, or a mixture of trans-1,2-dichloroethylene and C₄F₉OC₂H₅.

TABLE 2 Synonym Name Chemical formula (or abbreviation) CAS registry number Halocarbons trichloroethylene CHCl═CCl₂ TCE 79-01-6 tetrachloroethylene CCl₂═CCl₂ PCE 127-18-4 (or perchloroethylene) n-propylbromide CH₃CH₂CH₂Br nPBr trans-1,2- CHCl═CHCl t-DCE 156-60-5 dichloroethylene Alcohols methanol CH₃OH MeOH 67-56-1 ethanol CH₃CH₂OH EtOH 64-17-5 n-propanol CH₃CH₂CH₂OH n-PrOH 71-23-8 isopropanol CH₃CH(OH)CH₃ IPA 67-63-0 Fluoroethers mixture of isomers- CF₃CF₂CF₂CF₂OCH₃ C₄F₉OCH₃ 163702-07-6 1,1,1,2,2,3,3,4,4- and (CF₃)₂CFCF₂OCH₃ and nonafluoro-4- 163702-08-7 methoxybutane and 2-(methoxy- difluoromethyl)- 1,1,1,2,3,3,3- heptafluoropropane mixture of isomers- CF₃CF₂CF₂CF₂OC₂H₅ and C₄F₉OC₂H₅ 163702-05-4 1-ethoxy- (CF₃)₂CFCF₂OC₂H₅ and 1,1,2,2,3,3,4,4,4- 163702-06-5 nonafluorobutane and 2-(ethoxy- difluoromethyl)- 1,1,1,2,3,3,3- heptafluoropropane Hydrofluorocarbons 1,1,1,2,3,4,4,5,5,5- CF₃CHFCHFCF₂CF₃ HFC-43-10mee decafluoropentane 1,1,1,3,3- CF₃CH₂CF₂CH₃ HFC-365mfc pentafluorobutane

The compounds listed in Table 2 are commercially available from chemical supply houses. C₄F₉OCH₃, and C₄F₉OC₂H₅are available from 3M™ (St. Paul, Minn.). HFC-43-10mee is available from E.I. DuPont de Nemours & Co (Wilmington, Del.). HFC-365mfc is available from Solvay-Solexis.

The compositions of the present invention may be prepared by any convenient method by combining the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combining the components in an appropriate vessel. Agitation may be used, if desired.

The compositions of the present invention comprise compositions containing one of the fluoroolefins listed in Table 1, PEIK, or PFBE, and at least one of the compounds selected from the group consisting of: trichloroethylene; tetrachloroethylene; trans-1,2-dichloroethylene; n-propylbromide; methanol; ethanol; n-propanol; isopropanol; C₄F₉OCH₃; C₄F₉OC₂H₅; HFC-43-10mee; HFC-365mfc; and combinations thereof. In one embodiment, the compositions are azeotropic or azeotrope-like. The exception thereto being that according to the compositions of the present invention, PFBE is not combined with an alcohol, trans-1,2-dichloroethylene alone, C₄F₉OCH₃ alone, HFC-43-10mee alone, HFC-365mfc alone, or a mixture of trans-1,2-dichloroethylene or C₄F₉OC₂H₅.

As used herein, an azeotropic composition is a constant boiling liquid admixture of two or more substances wherein the admixture distills without substantial composition change and behaves as a constant boiling composition. Constant boiling compositions, which are characterized as azeotropic, exhibit either a maximum or a minimum boiling point, as compared with that of the non-azeotropic mixtures of the same substances. Azeotropic compositions as used herein include homogeneous azeotropes which are liquid admixtures of two or more substances that behave as a single substance, in that the vapor, produced by partial evaporation or distillation of the liquid, has the same composition as the liquid. Azeotropic compositions as used herein also include heterogeneous azeotropes where the liquid phase splits into two or more liquid phases. In these embodiments, at the azeotropic point, the vapor phase is in equilibrium with two liquid phases and all three phases have different compositions. If the two equilibrium liquid phases of a heterogeneous azeotrope are combined and the composition of the overall liquid phase calculated, this would be identical to the composition of the vapor phase.

As used herein, the term “azeotrope-like composition” also sometimes referred to as “near azeotropic composition,” means a constant boiling, or substantially constant boiling liquid admixture of two or more substances that behaves as a single substance. One way to characterize an azeotrope-like composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled. That is, the admixture distills/refluxes without substantial composition change. Another way to characterize an azeotrope-like composition is that the bubble point vapor pressure of the composition and the dew point vapor pressure of the composition at a particular temperature are substantially the same. Herein, a composition is azeotrope-like if, after 50 weight percent of the composition is removed such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed by evaporation or boil off is less than 10 percent.

In cleaning apparati, such as vapor degreasers or defluxers, some loss of the cleaning compositions may occur during operation through leaks in shaft seals, hose connections, soldered joints and broken lines. In addition, the working composition may be released to the atmosphere during maintenance procedures on equipment. If the composition is not a pure compound or azeotropic or azeotrope-like composition, the composition may change when leaked or discharged to the atmosphere from the equipment, which may cause the composition remaining in the equipment to become flammable or to exhibit unacceptable performance. Accordingly, it is desirable to use as a cleaning composition a single fluorinated hydrocarbon or an azeotropic or azeotrope-like composition that fractionates to a negligible degree upon leak or boil-off.

The azeotropic compositions of one embodiment of the present invention are listed in Table 3.

TABLE 3 Comp A Comp B wt % A wt % B T (C.) F14E methanol 85.1 14.9 59.1 F14E isopropanol 87.1 12.9 66.9 F14E ethanol 87.9 12.1 65.2 F14E t-DCE 44.3 55.7 44.0 F14E nPBr 54.4 45.6 66.6 F24E methanol 72.1 27.9 63.4 F24E isopropanol 78.1 21.9 74.1 F24E ethanol 79.2 20.8 71.8 F24E t-DCE 24.5 75.5 45 F24E nPBr 25.7 74.3 70.2 F24E PCE 85.2 14.8 89.9 F24E TCE 65.0 35.0 75.9 PEIK methanol 97.0 3.0 43.5 PEIK isopropanol 96.7 3.3 45.5 PEIK ethanol 96.8 3.2 44.7 PEIK t-DCE 72.9 27.1 34.7 PEIK 43-10mee 73.2 26.8 47.7 PEIK 365mfc 38.8 61.2 38.1 PFBE methanol 92.2 7.8 50.6 PFBE isopropanol 95.2 4.8 56.3 PFBE ethanol 94.8 5.2 55.2 PFBE t-DCE 52.8 47.2 41.3 PFBE nPBr 82.3 17.7 57.1 F22E methanol 95.8 4.2 43.7 F22E isopropanol 98.0 2.0 47.2 F22E ethanol 97.6 2.4 46.6 F22E t-DCE 71.0 29.0 33.9 F22E nPBr 87.0 13.0 43.3 F22E 43-10mee 89.8 10.2 47.9 F22E 365mfc 29.3 70.7 39.2 F13iE methanol 95.5 4.5 44.4 F13iE isopropanol 97.8 2.2 48.0 F13iE ethanol 97.4 2.6 47.5 F13iE t-DCE 70.2 29.8 34.4 F13iE nPBr 86.4 13.6 44.0 F13iE 43-10mee 95.3 4.7 48.8 F13iE 365mfc 24.6 75.4 39.5 F3i3iE methanol 85.0 15.0 59.8 F3i3iE isopropanol 89.2 10.8 70.0 F3i3iE ethanol 89.0 11.0 67.8 F3i3iE t-DCE 44.1 55.9 44.5 F3i3iE C₄F₉OC₂H₅ 22.8 77.2 75.7 F3i3iE nPBr 67.4 32.6 61.3 F13E methanol 94.4 5.6 47.3 F13E isopropanol 96.9 3.1 51.9 F13E ethanol 96.5 3.5 51.1 F13E t-DCE 66.3 33.7 36.3 F13E nPBr 83.7 16.3 47.1 F13E 43-10mee 59.5 40.5 52.3 F3i4E t-DCE 7.6 92.4 47.6 F3i4E methanol 42.8 57.2 65.4 F3i4E isopropanol 57.8 42.2 81.0 F3i4E ethanol 58.7 41.3 77.3 F3i4E nPBr 31.9 68.1 69.6 F44E nPBr 8.1 91.9 70.9

Additionally in another embodiment, the azeotropic compositions of the present invention may include ternary and quarternary azeotropic compositions comprising compounds from Table 2. Examples without limitation of these higher order azeotropic compositions are exemplified in Table 4 along with the atmospheric pressure boiling points for the compositions.

TABLE 4 Comp A Comp B Comp C wt % A wt % B wt % C T(° C.) F14E t-DCE methanol 34.4 59.0 6.6 39.9 F14E t-DCE ethanol 41.9 55.1 3.0 43.2 F24E t-DCE methanol 10.3 80.3 9.4 41.0 F24E t-DCE ethanol 24.8 70.9 4.3 43.0 PEIK t-DCE methanol 71.5 26.4 2.1 33.0 PEIK t-DCE ethanol 73.0 25.7 1.3 34.2 PEIK t-DCE 43-10mee 57.0 26.9 16.1 34.3 PEIK t-DCE 365mfc 43.7 24.1 32.2 32.6 PFBE t-DCE C₄F₉OCH₃ 40.1 47.5 12.4 41.3 F22E t-DCE methanol 67.9 29.7 2.4 32.6 F22E t-DCE 365mfc 45.4 27.2 27.4 33.0 F13iE t-DCE methanol 66.9 30.6 2.5 33.0 F13iE t-DCE 43-10mee 69.8 29.8 0.4 34.4 F13iE t-DCE 365mfc 41.9 27.8 30.3 33.3 F3i3iE t-DCE methanol 32.9 60.2 6.9 40.1 F3i3iE t-DCE ethanol 41.1 56.3 2.6 43.8 F13E t-DCE methanol 62.2 34.7 3.1 34.5 F13E t-DCE 43-10mee 48.0 33.2 18.8 36.1 F13E t-DCE 365mfc 23.1 30.3 46.6 34.4

The binary azeotrope-like compositions of the present invention are listed in Table 5.

TABLE 5 Comp A Comp B wt % A wt % B T (C.) F14E Methanol 60-99 1-40 59.1 F14E Isopropanol 70-99 1-30 66.9 F14E Ethanol 72-99 1-28 65.2 F14E t-DCE  1-75 25-99  44.0 F14E nPBr  1-99 1-99 66.6 F14E C₄F₉OCH₃  1-99 1-99 50 F14E C₄F₉OC₂H₅  1-99 1-99 50 F14E 43-10mee  1-99 1-99 50 F24E Methanol  1-91 9-99 63.4 F24E Isopropanol 57-91 9-43 74.1 F24E Ethanol 57-92 8-43 71.8 F24E t-DCE  1-63 37-99  46.1 F24E nPBr  1-70 30-99  70.2 F24E PCE 61-99 1-39 89.9 F24E TCE 40-84 16-60  75.9 F24E C₄F₉OC₂H₅  1-99 1-99 50 PEIK Methanol 91-99 1-9  43.5 PEIK Isopropanol 57-99 1-16 45.5 PEIK Ethanol 85-99 1-15 44.7 PEIK t-DCE 50-88 12-50  34.7 PEIK 4310mcee  1-99 1-99 47.7 PEIK 365mfc  1-99 1-99 38.1 PEIK C₄F₉OCH₃  1-99 1-99 50 PFBE Methanol 80-99 1-20 50.6 PFBE Isopropanol 83-99 1-17 56.3 PFBE Ethanol 83-99 1-17 55.2 PFBE t-DCE 21-79 21-79  41.3 PFBE nPBr 44-99 1-55 57.1 PFBE C₄F₉OCH₃  1-99 1-99 50 PFBE C₄F₉OC₂H₅  1-99 1-99 50 PFBE 43-10mee  1-99 1-99 50 PFBE 365mfc  1-99 1-99 50 F22E Methanol 86-99 1-14 43.7 F22E Isopropanol 88-99 1-12 47.2 F22E Ethanol 88-99 1-12 46.6 F22E t-DCE 48-87 13-52  33.9 F22E nPBr 64-99 1-36 43.3 F22E 43-10mee  1-99 1-99 47.9 F22E 365mfc  1-99 1-99 39.2 F22E C₄F₉OCH₃  1-99 1-99 50 F13iE Methanol 86-99 1-14 44.4 F13iE Isopropanol 87-99 1-13 48.0 F13iE Ethanol 88-99 1-12 47.5 F13iE t-DCE 46-86 14-54  34.4 F13iE nPBr 64-99 1-36 44.0 F13iE 43-10mee  1-99 1-99 48.8 F13iE 365mfc  1-99 1-99 39.5 F13iE C₄F₉OCH₃  1-99 1-99 50 F3i3iE Methanol 57-99 1-43 59.8 F3i3iE Isopropanol 73-99 1-27 70.0 F3i3iE Ethanol 73-99 1-27 67.8 F3i3iE t-DCE  1-76 24-99  44.5 F3i3iE C₄F₉OC₂H₅  1-99 1-99 75.7 F3i3iE nPBr 43-86 14-57  61.3 F3i3iE C₄F₉OCH₃  1-99 1-99 50 F13E Methanol 84-99 1-16 47.3 F13E Isopropanol 86-99 1-14 51.9 F13E Ethanol 86-99 1-14 51.1 F13E t-DCE 42-84 16-58  36.3 F13E nPBr 61-99 1-39 47.1 F13E 43-10mee  1-99 1-99 52.3 F13E C₄F₉OCH₃  1-99 1-99 50 F13E C₄F₉OC₂H₅  1-99 1-99 50 F13E 365mfc  1-99 1-99 50 F3i4E t-DCE  1-69 31-99  47.6 F3i4E Methanol  1-89 11-99  65.4 F3i4E Isopropanol  1-88 12-99  81 F3i4E Ethanol  1-89 11-99  77.3 F3i4E nPBr  1-72 28-99  69.6 F44E nPBr  1-70 30-99  70.9

In addition to the binary azeotrope-like compositions in the preceding table, higher order (ternary or quarternary) azeotrope-like compositions are included in the present invention. Examples without limitation of ternary or higher order azeotrope-like compositions are given in Table 6.

TABLE 6 Comp A Comp B Comp C wt % A wt % B wt % C T(° C.) F14E t-DCE C₄F₉OCH₃  1-70 20-70  1-70 50 F14E t-DCE C₄F₉OC₂H₅  1-70 29-90  1-60 50 F14E t-DCE 43-10mee  1-80 15-60  1-80 50 F14E t-DCE 365mfc  1-70 10-60  1-80 50 F14E t-DCE Methanol  1-70 29-98  1-30 39.9 F14E t-DCE ethanol  1-70 29-98  1-20 43.2 F24E t-DCE C₄F₉OCH₃  1-70 20-70  1-70 50 F24E t-DCE C₄F₉OC₂H₅  1-60 30-80  1-60 50 F24E t-DCE Methanol  1-50 40-98  1-25 41.0 F24E t-DCE ethanol  1-60 39-98  1-20 45.0 PEIK t-DCE C₄F₉OCH₃  1-70 20-50  1-70 50 PEIK t-DCE Methanol 50-85 14-49 1-9 33.0 PEIK t-DCE ethanol 50-85 14-49 1-9 34.2 PEIK t-DCE 43-10mee  1-85 10-65  1-80 34.3 PEIK t-DCE 365mfc  1-85  1-55  1-85 32.6 PFBE t-DCE 43-10mee  1-70 20-60  1-79 50 PFBE t-DCE 365mfc  1-70 15-60  1-80 50 PFBE t-DCE C₄F₉OCH₃  1-75 24-75  1-70 41.3 F22E t-DCE C₄F₉OCH₃  1-70 29-70  1-70 50 F22E t-DCE 43-10mee  1-80 19-60  1-80 50 F22E t-DCE Methanol 45-85 14-54  1-10 32.6 F22E t-DCE 365mfc  1-89 10-60  1-85 33.0 F13iE t-DCE C₄F₉OCH₃  1-75 24-70  1-70 50 F13iE t-DCE Methanol 45-85 14-54  1-10 33.0 F13iE t-DCE 43-10mee  1-89 10-60  1-80 34.4 F13iE t-DCE 365mfc  1-89 10-60  1-84 33.3 F3i3iE t-DCE Methanol  1-70 29-95  1-25 40.1 F3i3iE t-DCE ethanol  1-65 34-98  1-15 43.8 F3i3iE t-DCE C₄F₉OCH₃  1-69 30-70  1-69 50 F3i3iE t-DCE C₄F₉OC₂H₅  1-69 30-80  1-69 50 F13E t-DCE Methanol 45-80 19-54  1-10 34.5 F13E t-DCE 43-10mee  1-85 14-60  1-80 36.1 F13E t-DCE 365mfc  1-85 14-60  1-80 34.4 F13E t-DCE C₄F₉OCH₃  1-80 19-70  1-70 50 F3i4E t-DCE C₄F₉OCH₃  1-30 25-69 30-69 50 F3i4E t-DCE C₄F₉OC₂H₅  1-50 30-98  1-60 50 F44E t-DCE C₄F₉OC₂H₅  1-70  1-60 29-98 50

In yet another embodiment of the invention, the compositions of the present invention may further comprise an aerosol propellant. Aerosol propellants may assist in delivering the present compositions from a storage container to a surface in the form of an aerosol. Aerosol propellant is optionally included in the present compositions in up to 25 weight percent of the total composition. Representative aerosol propellants comprise air, nitrogen, carbon dioxide, difluoromethane (HFC-32, CH₂F₂), trifluoromethane (HFC-23, CHF₃), difluoroethane (HFC-152a, CHF₂CH₃), trifluoroethane (HFC-143a, CH₃CF₃; or HFC-143, CHF₂CH₂F), tetrafluoroethane (HFC-134a, CF₃CH₂F; HFC-134, CHF₂CHF₂), pentafluoroethane (HFC-125, CF₃CHF₂), heptafluoropropane (HFC-227ea, CF₃CHFCF₃), pentafluoropropane (HFC-245fa, CF₃CH₂CHF₂), dimethyl ether (CH₃OCH₃), or mixtures thereof.

In an embodiment of the invention, the present inventive azeotropic compositions are effective cleaning agents, defluxers and degreasers. In particular, the present inventive azeotropic compositions are useful when de-fluxing circuit boards with components such as Flip chip, μBGA (ball grid array), and Chip scale or other advanced high-density packaging components. Flip chips, μBGA, and Chip scale are terms that describe high density packaging components used in the semi-conductor industry and are well understood by those working in the field.

In another embodiment the present invention relates to a process for removing residue from a surface or substrate, comprising: contacting the surface or substrate with a composition of the present invention and recovering the surface or substrate from the composition.

In a process embodiment of the invention, the surface or substrate may be an integrated circuit device, in which case, the residue comprises rosin flux or oil. The integrated circuit device may be a circuit board with various types of components, such as Flip chips, μBGAs, or Chip scale packaging components. The surface or substrate may additionally be a metal surface such as stainless steel. The rosin flux may be any type commonly used in the soldering of integrated circuit devices, including but not limited to RMA (rosin mildly activated), RA (rosin activated), WS (water soluble), and OA (organic acid). Oil residues include but are not limited to mineral oils, motor oils, and silicone oils.

In the inventive process, the means for contacting the surface or substrate is not critical and may be accomplished by immersion of the device in a bath containing the composition, spraying the device with the composition or wiping the device with a substrate that has been wet with the composition. Alternatively, the composition may also be used in a vapor degreasing or defluxing apparatus designed for such residue removal. Such vapor degreasing or defluxing equipment is available from various suppliers such as Forward Technology (a subsidiary of the Crest Group, Trenton, N.J.), Trek Industries (Azusa, Calif.), and Ultronix, Inc. (Hatfield, Pa.) among others.

An effective composition for removing residue from a surface would be one that had a Kauri-Butanol value (Kb) of at least about 10, preferably about 40, and even more preferably about 100. The Kauri-Butanol value (Kb) for a given composition reflects the ability of said composition to solubilize various organic residues (e.g., machine and conventional refrigeration lubricants). The Kb value may be determined by ASTM D-1133-94.

The following specific examples are meant to merely illustrate the invention, and are not meant to be limiting in any way whatsoever.

Examples Example 1 Synthesis of 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene (F14E) Synthesis of C₄F₉CH₂CHICF₃

Perfluoro-n-butyliodide (180.1 gm, 0.52 moles) and 3,3,3-trifluoropropene (25.0 gm, 0.26 moles) were added to a 400 ml Hastelloy™ shaker tube and heated to 200° C. for 8 hours under autogenous pressure which increased to a maximum of 428 PSI. After cooling the reaction vessel to room temperature, the product was collected. The product of this reaction and two others carried out in substantially the same manner, except that one of the reactions had twice the quantity of reactants, were combined and distilled to give 322.4 gm of C₄F₉CH₂CHICF₃ (52.2° C./35 mm,70% yield).

Conversion of C₄F₉CH₂CHICF₃ to F14E

A 2 liter round bottom flask equipped with a stirring bar and packed distillation column and still head was charged with isopropyl alcohol (95 ml), KOH (303.7 gm, 0.54 moles) and water (303 ml). C₄F₉CH₂CHICF₃ (322.4 gm, 0.73 mole) was added dropwise via addition funnel to the aqueous KOH/IPA mixture at room temperature. The reaction was then heated to 65-70° C. to recover the product by distillation, The distillated was collected, washed with sodium metabisulfite and water, dried over MgSO₄ and then distilled through a 6-inch (15.2 cm) column packed with glass helices. The product, F14E (173.4 gm, 76% yield), boils at 78.2° C. It was characterized by NMR spectroscopy (¹⁹F: δ −66.7 (CF₃, m, 3F), −81.7 (CF₃, m, 3F), −124.8 (CF₂, m, 2F), −126.4 (CF₂, m, 2F), −114.9 ppm (CF₂, m, 2F); ¹H: 6.58d)

Example 2 Synthesis of 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene (F24E) Synthesis of C₄F₉CHICH₂C₂F₅

Perfluoroethyliodide (220 gm, 0.895 mole) and 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene (123 gm, 0.50 mole) were added to a 400 ml Hastelloy™ shaker tube and heated to 200° C. for 10 hours under autogenous pressure. The product from this and two others carried out under substantially similar conditions were combined and washed with two 200 mL portions of 10 wt % aqueous sodium bisulfite. The organic phase was dried over calcium chloride and then distilled to give 277.4 gm of C₄F₉CH₂CHICF₃ (79-81° C./67-68 mm Hg) in 37% yield.

Conversion of C₄F₉CHICH₂C₂F₅ to F24E

A 1 L round bottom flask equipped with a mechanical stirrer, addition funnel, condenser, and thermocouple was charged with C₄F₉CHICH₂C₂F₅ (277.4 gm, 0.56 moles) and isopropanol (217.8 g). The addition funnel was charged with a solution of potassium hydroxide (74.5 g, 1.13 moles) dissolved in 83.8 g of water. The KOH solution was added dropwise to the flask with rapid stirring over the course of about one hour as the temperature slowly increased from 21° C. to 42° C. The reaction mass was diluted with water and the product recovered by phase separation. The product was washed with 50 mL portions of 10 wt aqueous sodium bisulfite and water, dried over calcium chloride, and then distilled at atmospheric pressure. The product, F24E (128.7 gm, 63%) boils at 95.5° C. and was characterized by NMR (¹⁹F: δ −81.6 (CF₃, m, 3F), −85.4(CF₃, m 3F), −114.7 (CF₂, m, 2F), −118.1 (CF₂, m, 2F), −124.8 ppm (CF₂, m, 2F), −126.3 ppm (CF₂, m, 2F); ¹H: δ6.48; chloroform-d solution).

Example 3 Synthesis of 1,1,1,4,5,5,5-Heptafluoro-4-(trifluoromethyl)-pent-2-ene (F13iE) Synthesis of CF₃CHICH₂CF(CF₃)₂

(CF₃)₂CFI (265 gm, 0.9 moles) and 3,3,3-trifluoropropene (44.0 gm, 0.45 moles) were added to a 400 ml Hastelloy™ shaker tube and heated to 200° C. for 8 hours under autogenous pressure which increased to a maximum of 585 psi. The product was collected at room temperature to give 110 gm of (CF₃)₂CFCH₂CHICF₃ (76-77° C./200 mm) in 62% yield.

Conversion of (CF₃)₂CFCH₂CHICF₃ to F13iE

A 500 ml round bottom flask equipped with a stirring bar and connected to a short path distillation column and dry ice trap was charged with isopropyl alcohol (50 ml), KOH (109 gm, 1.96 moles) and water (109 ml). The mixture was heated to 42° C. and (CF₃)₂CFCH₂CHICF₃ (109 gm, 0.28 moles) was added dropwise via an addition funnel. During the addition, the temperature increased from 42 to 55° C. After refluxing for 30 minutes, the temperature in the flask increased to 62° C. and the product was collected by distillation. The product was collected, washed with water, dried with MgSO₄, and distilled. The product, F13iE (41 gm, 55% yield), boils at 48-50° C. and was characterized by NMR (19F: δ −187.6 (CF, m 1F), −77.1 (CF3, m 6F), −66.3 (CF3, m 3F); chloroform-d solution).

Example 4 Synthesis of C4F9CHICH2C2F5

3,3,4,4,5,5,6,6,6-Nonafluorohex-1-ene (20.5 gm, 0.0833 mole), bis(triphenyl phosphine)nickel(0) dicarbonyl (0.53 g, 0.0008 mole), and perfluoroethyliodide (153.6 gm, 0.625 mole) were added to a 210 ml Hastelloy™ shaker tube and heated at 100° C. for 8 hours under autogenous pressure. Analysis of the product by GC-MS indicated the presence of C4F9CHICH2C2F5 (64.3 GC area %) and the diadduct (3.3 GC area %); the conversion of 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene was 80.1%.

Example 5 De-Fluxing

The compositions of the present invention are effective for cleaning ionic contamination (flux residue) from a surface. The test used to determine surface cleanliness involved the following steps:

-   1. A rosin flux was painted liberally onto a FR-4 test board (an     epoxy printed wiring board with tracing made of tinned copper). -   2. The board so treated was then heated in an oven at about 175° C.     for about 1-2 minutes to activate the rosin flux. -   3. The board was then immersed in solder (Sn63, a 63/37 Sn/lead     solder) at about 200° C. for about 10 seconds. -   4. The board was then cleaned by immersion in the boiling cleaning     composition for about 3 minutes and providing gentle movement of the     board. The board was then immersed in a fresh, room temperature bath     of cleaning composition to rinse for about 2 minutes. -   5. The board was then tested for residual ionics with an Omega Meter     600 SMD ionic analyzer.

The cleaning performance was determined by weighing the board prior to deposition of the flux, after the deposition of the flux and then after the cleaning procedure. The results are given in Table 7.

TABLE 7 Composition Dry weight Wet weight Post dry weight % (wt %) (grams) (grams) (grams) soil removed PEIK/t- 5.4951 5.5689 5.5010 92% DCE/MeOH 5.0578 5.1401 5.0613 96% (71.5/26.4/ 5.4815 5.5554 5.4846 96% 2.1) 3.3450 5.4124 5.3483 95% Average 95%

Example 6 Metal Cleaning

Stainless steel (type 316) 2″×3″ coupons that have been grit blasted to provide an unpolished surface were pre-cleaned and oven dried to remove any residual soil. The tare weight of each coupon was determined to 0.1 mg. A small amount of mineral oil was applied with a swab, the coupon was then re-weighed to obtain the “loaded” weight. The coupon was then cleaned by immersion into a boiling cleaning composition for 1 minute, held in vapor for 30 seconds and then air dried for 1 minute. The coupon was then re-weighed and the percent of soil removed calculated using the 3 recorded weights. The results are shown in Table 8.

TABLE 8 Post Dry Composition Dry weight Wet weight weight Percent Soil (wt %) (grams) (grams) (grams) removed PEIK/t-DCE 21.588 21.6238 21.5881 100 (72.9/27.1) 21.5882 21.62.17 21.5877 101 21.2181 21.3160 21.2180 100 Average 100

The results show efficient removal of mineral oil residue from stainless steel surfaces by the compositions of the present invention.

Example 7 Metal Cleaning

Stainless steel (type 316) 2″×3″ coupons that have been grit blasted to provide an unpolished surface were pre-cleaned and oven dried to remove any residual soil. The tare weight of each coupon was determined to 0.1 mg. A small amount of DC 200 Silicone was applied with a swab, the coupon was then re-weighed to obtain the “loaded” weight. The coupon was then cleaned by immersion into a boiling cleaning composition for 1 minute, held in vapor for 30 seconds and then air dried for 1 minute. The coupon was then weighed and the percent of soil removed is calculated using the 3 recorded weights. The results are shown in Table 9.

TABLE 9 Post Dry Composition Dry weight Wet weight weight Percent Soil (wt %) (grams) (grams) (grams) removed PEIK/t-DCE 21.2183 21.26343 21.2183 100 (72.9/27.1) 19.0196 19.0461 19.0198 99 21.3960 21.4480 21.3963 99 Average 100

The results show efficient removal of silicone residue from stainless steel surfaces by the compositions of the present invention.

Example 8 Metal Cleaning Efficacy

Stainless steel (type 316) 2″×3″ coupons that have been grit blasted to provide an unpolished surface were pre-cleaned and oven dried to remove any residual soil. Each coupon was weighed to 4 places to obtain a tare weight. A small amount of mineral oil was applied with a swab, the coupon is then weighed to obtain the “loaded” weight. The coupon was then cleaned by immersion into a boiling cleaning composition for 1 minute, held in vapor for 30 seconds and then air dried for 1 minute. The coupon was then weighed and the percent of soil removed is calculated using the 3 recorded weights. The results are shown in Table 10.

TABLE 10 Post Dry Composition Dry weight Wet weight weight Percent Soil (wt %) (grams) (grams) (grams) removed PEIK/MeOH 21.2968 21.3525 21.3029 89 (97.0/3.0) 21.2470 21.62678 21.2530 71 21.5313 21.5656 21.5417 70 Average 77

The results show efficient removal of mineral oil residue from stainless steel surfaces by the compositions of the present invention.

Example 9 Metal Cleaning Efficacy

Stainless steel (type 316) 2″×3″ coupons that have been grit blasted to provide an unpolished surface were pre-cleaned and oven dried to remove any residual soil. Each coupon was weighed to 4 places to obtain a tare weight. A small amount of DC 200 Silicone was applied with a swab, the coupon is then weighed to obtain the “loaded” weight. The coupon was then cleaned by immersion into a boiling cleaning composition for 1 minute, held in vapor for 30 seconds and then air dried for 1 minute. The coupon was then weighed and the percent of soil removed is calculated using the 3 recorded weights. The results are shown in Table 11.

TABLE 11 Post Dry Composition Dry weight Wet weight weight Percent Soil (wt %) (grams) (grams) (grams) removed PEIK/MeOH 20.9536 20.9902 20.9536 100 (97.0/3.0) 21.1531 21.1889 21.1528 101 20.6276 20.6735 20.6285 98 Average 100

Example 10 Metal Cleaning Efficacy

Stainless steel (type 316) 2″×3″ coupons that have been grit blasted to provide an unpolished surface were pre-cleaned and oven dried to remove any residual soil. Each coupon was weighed to 4 places to obtain a tare weight. A small amount of mineral oil was applied with a swab, the coupon is then weighed to obtain the “loaded” weight. The coupon was then cleaned by immersion into a boiling cleaning composition for 1 minute, held in vapor for 30 seconds and then air dried for 1 minute. The coupon was then weighed and the percent of soil removed is calculated using the 3 recorded weights. The results are shown in Table 12.

TABLE 12 Post Dry Composition Dry weight Wet weight weight Percent Soil (wt %) (grams) (grams) (grams) removed F24E/t-DCE 21.6977 21.7396 21.6972 101 (24.2/75.8) 19.0213 19.0848 19.0207 101 21.2883 21.3127 21.2874 104 21.5190 21.5599 21.5183 102 21.5046 21.5438 21.5036 103 Average 102

Example 11 Metal Cleaning Efficacy

Stainless steel (type 316) 2″×3″ coupons that have been grit blasted to provide an unpolished surface were pre-cleaned and oven dried to remove any residual soil. Each coupon was weighed to 4 places to obtain a tare weight. A small amount of DC 200 Silicone oil was applied with a swab, the coupon is then weighed to obtain the “loaded” weight. The coupon was then cleaned by immersion into a boiling cleaning composition for 1 minute, held in vapor for 30 seconds and then air dried for 1 minute. The coupon was then weighed and the percent of soil removed is calculated using the 3 recorded weights. The results are shown in Table 13.

TABLE 13 Post Dry Composition Dry weight Wet weight weight Percent Soil (wt %) (grams) (grams) (grams) removed F24E/t-DCE 21.6973 21.817 21.7333 70 (24.2/75.8) 19.0203 19.1243 19.0263 94 21.5040 21.5912 21.5193 82 21.5183 21.5977 21.5230 94 21.2873 21.3495 21.2909 94 Average 87

The results show efficient removal of silicone residue from stainless steel surfaces by the compositions of the present invention.

Example 12

A mixture of 21.8% F24E and 78.2% 1,2-trans-dichloroethylene (t-DCE) by weight was prepared and placed into a 5-plate distillation apparatus, with a 10:1 reflux ratio. The temperature at the distillation head was recorded and several cuts of the distilled material were removed over time. Distilled material was analyzed by gas chromatography. Data is shown in table 14 below. Composition and temperature remained stable throughout the experiment, indicating azeotropic behavior of this mixture.

TABLE 14 Distillation cut Head temp (C.) Wt % distilled % F24E % t-DCE 1 45 8 24.5 75.6 2 45 15 24.3 75.7 3 45 22 24.2 75.8 4 45 28 24.2 75.8

Example 13

A mixture of 20.0% F24E, 75.8% 1,2-trans-dichloroethylene (t-DCE) and 4.2% ethanol by weight was prepared and placed into a 5-plate distillation apparatus, with a 10:1 reflux ratio. The temperature at the distillation head was recorded and several cuts of the distilled material were removed over time. Distilled material was analyzed by gas chromatography. Data is shown in table 15 below. Composition and temperature remained stable throughout the experiment, indicating azeotropic behavior of this mixture.

TABLE 15 Head temp Wt % Distillation cut (°C.) distilled % F24E % t-DCE % EtOH 1 43 13 24.8 71.0 4.3 2 43 19 25.3 70.4 4.3 3 43 25 24.8 70.8 4.3 4 43 32 24.8 70.9 4.3 5 43 40 24.9 70.8 4.3 6 43 47 24.8 70.9 4.3 

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 11. (canceled)
 12. An azeotropic or azeotrope-like composition comprising an azeotropic or azeotrope-like composition selected from the group consisting of: about 60 to about 99 weight percent F14E and about 1 to about 40 weight percent methanol; about 70 to about 99 weight percent F14E and about 1 to about 30 weight percent isopropanol; about 72 to about 99 weight percent F14E and about 1 to about 28 weight percent ethanol; about 1 to about 75 weight percent F14E and about 25 to about 99 weight percent trans-1,2-dichloroethylene; about 1 to about 99 weight percent F14E and about 99 to about 1 weight percent n-propylbromide; about 1 to about 99 weight percent F14E and about 99 to about 1 weight percent C₄F₉OCH₃; about 1 to about 99 weight percent F14E and about 99 to about 1 weight percent C₄F₉OC₂H₅; about 1 to about 99 weight percent F14E and about 99 to about 1 weight percent HFC43-10mee; about 1 to about 91 weight percent F24E and about 99 to about 9 weight percent methanol; about 57 to about 91 weight percent F24E and about 43 to about 9 weight percent isopropanol; about 1 to about 70 weight percent F24E and about 99 to about 30 weight percent n-propylbromide; about 61 to about 99 weight percent F24E and about 39 to about 1 weight percent perchloroethylene; about 40 to about 84 weight percent F24E and about 60 to about 16 weight percent trichloroethylene; about 1 to about 99 weight percent F24E and about 99 to about 1 weight percent C₄F₉OC₂H₅; about 86 to about 99 weight percent F22E and about 14 to about 1 weight percent methanol; about 88 to about 99 weight percent F22E and about 12 to about 1 weight percent isopropanol; about 88 to about 99 weight percent F22E and about 12 to about 1 weight percent ethanol; about 48 to about 87 weight percent F22E and about 52 to about 13 weight percent trans-1,2-dichloroethylene; about 64 to about 99 weight percent F22E and about 36 to about 1 weight percent n-propylbromide; about 1 to about 99 weight percent F22E and about 99 to about 1 weight percent HFC-43-10mee; about 1 to about 99 weight percent F22E and about 99 to about 1 weight percent HFC-365mfc; about 1 to about 99 weight percent F22E and about 99 to about 1 weight percent C₄F₉OCH₃; about 86 to about 99 weight percent F13iE and about 14 to about 1 weight percent methanol; about 87 to about 99 weight percent F13iE and about 13 to about 1 weight percent isopropanol; about 46 to about 86 weight percent F13iE and about 54 to about 14 weight percent trans-1,2-dichloroethylene; about 64 to about 99 weight percent F13iE and about 36 to about 1 weight percent n-propylbromide; about 1 to about 99 weight percent F13iE and about 99 to about 1 weight percent HFC-43-10mee; about 1 to about 99 weight percent F13iE and about 99 to about 1 weight percent HFC-365mfc; about 1 to about 99 weight percent F13iE and about 99 to about 1 weight percent C₄F₉OCH₃; about 57 to about 99 weight percent F3i3iE and about 43 to about 1 weight percent methanol; about 73 to about 99 weight percent F3i3iE and about 27 to about 1 weight percent isopropanol; about 73 to about 99 weight percent F3i3iE and about 27 to about 1 weight percent ethanol; about 1 to about 76 weight percent F3i3iE and about 99 to about 24 weight percent trans-1,2-dichloroethylene; about 1 to about 99 weight percent F3i3iE and about 99 to about 1 weight percent C₄F₉OC₂H₅; about 43 to about 86 weight percent F3i3iE and about 57 to about 14 weight percent n-propylbromide; about 1 to about 99 weight percent F3i3iE and about 99 to about 1 weight percent C₄F₉OCH₃; about 84 to about 99 weight percent F13E and about 16 to about 1 weight percent methanol; about 86 to about 99 weight percent F13E and about 14 to about 1 weight percent isopropanol; about 86 to about 99 weight percent F13E and about 14 to about 1 weight percent ethanol; about 42 to about 84 weight percent F13E and about 58 to about 16 weight percent trans-1,2-dichloroethylene; about 61 to about 99 weight percent F13E and about 39 to about 1 weight percent n-propylbromide; about 1 to about 99 weight percent F13E and about 99 to about 1 weight percent HFC-43-10mee; about 1 to about 99 weight percent F13E and about 99 to about 1 weight percent C₄F₉OCH₃; about 1 to about 99 weight percent F13E and about 99 to about 1 weight percent C₄F₉OC₂H₅; about 1 to about 99 weight percent F13E and about 99 to about 1 weight percent HFC365mfc; about 1 to about 69 weight percent F3i4E and about 99 to about 31 weight percent trans-1,2-dichloroethylene; about 1 to about 89 weight percent F3i4E and about 99 to about 11 weight percent methanol; about 1 to about 88 weight percent F3i4E and about 99 to about 12 weight percent isopropanol; about 1 to about 89 weight percent F3i4E and about 99 to about 11 weight percent ethanol; about 1 to about 72 weight percent F3i4E and about 99 to about 28 weight percent n-propylbromide; about 1 to about 70 weight percent F44E and about 99 to about 30 weight percent n-propylbromide; about 1 to about 70 weight percent F14E, about 29 to about 98 weight percent trans-1,2-dichloroethylene, and about 1 to about 30 weight percent methanol; about 1 to about 70 weight percent F14E, about 29 to about 98 weight percent trans-1,2-dichloroethylene, and about 1 to about 20 weight percent ethanol; about 1 to about 70 weight percent F14E, about 20 to about 70 weight percent trans-1,2-dichloroethylene, and about 1 to about 70 weight percent C₄F₉OCH₃; about 1 to about 70 weight percent F14E, about 29 to about 90 weight percent trans-1,2-dichloroethylene, and about 1 to about 60 weight percent C₄F₉OC₂H₅; about 1 to about 80 weight percent F14E, about 15 to about 60 weight percent trans-1,2-dichloroethylene, and about 1 to about 80 weight percent HFC-43-10mee; about 1 to about 70 weight percent F14E, about 10 to about 60 weight percent trans-1,2-dichloroethylene, and about 1 to about 80 weight percent HFC-365mfc; about 1 to about 50 weight percent F24E, about 40 to about 98 weight percent trans-1,2-dichloroethylene, and about 1 to about 25 weight percent methanol; about 1 to about 60 weight percent F24E, about 39 to about 98 weight percent trans-1,2-dichloroethylene, and about 1 to about 20 weight percent ethanol; about 1 to about 70 weight percent F24E, about 20 to about 70 weight percent trans-1,2-dichloroethylene, and about 1 to about 70 weight percent C₄F₉OCH₃; about 1 to about 60 weight percent F24E, about 30 to about 80 weight percent trans-1,2-dichloroethylene, and about 1 to about 60 weight percent C₄F₉OC₂H₅; about 45 to about 85 weight percent F22E, about 14 to about 54 weight percent trans-1,2-dichloroethylene, and about 1 to about 10 methanol; about 1 to about 89 weight percent F22E, about 10 to about 60 weight percent trans-1,2-dichloroethylene, and about 1 to about 85 HFC-365mfc; about 1 to about 70 weight percent F22E, about 29 to about 70 weight percent trans-1,2-dichloroethylene, and about 1 to about 70 C₄F₉OCH₃; about 1 to about 80 weight percent F22E, about 19 to about 60 weight percent trans-1,2-dichloroethylene, and about 1 weight percent to about Y80 weight percent HFC-43-10mee; about 45 to about 85 weight percent F13iE, about 14 to about 54 weight percent trans-1,2-dichloroethylene, and about 1 to about 10 weight percent methanol; about 1 to about 89 weight percent F13iE, about 10 to about 60 weight percent trans-1,2-dichloroethylene, and about 1 to about 80 weight percent HFC-43-10mee; about 1 to about 89 weight percent F13iE, about 10 to about 60 weight percent trans-1,2-dichloroethylene, and about 1 to about 84 weight percent HFC-365mfc; about 1 to about 75 weight percent F13iE, about 24 to about 70 weight percent trans-1,2-dichloroethylene, and about 1 to about 70 weight percent C₄F₉OCH₃; about 1 to about 70 weight percent F3i3iE, about 29 to about 95 weight percent trans-1,2-dichloroethylene, and about 1 to about 25 weight percent methanol; about 1 to about 65 weight percent F3i3iE, about 34 to about 98 weight percent trans-1,2-dichloroethylene, and about 1 to about 15 weight percent ethanol; about 1 to about 69 weight percent F3i3iE, about 30 to about 70 weight percent trans-1,2-dichloroethylene, and about 1 to about 69 weight percent C₄F₉OCH₃; about 1 to about 69 weight percent F3i3iE, about 30 to about 80 weight percent trans-1,2-dichloroethylene, and about 1 to about 69 weight percent C₄F₉OC₂H₅; about 45 to about 80 weight percent F13E, about 19 to about 54 weight percent trans-1,2-dichloroethylene, and about 1 to about 10 weight percent methanol; about 1 to about 85 weight percent F13E, about 14 to about 60 weight percent trans-1,2-dichloroethylene, and about 1 to about 80 weight percent HFC-43-10mee; about 1 to about 85 weight percent F13E, about 14 to about 60 weight percent trans-1,2-dichloroethylene, and about 1 to about 80 weight percent HFC-365mfc; about 1 to about 80 weight percent F13E, about 19 to about 70 weight percent trans-1,2-dichloroethylene, and about 1 to about 70 weight percent C₄F₉OCH₃; about 1 to about 30 weight percent F3i4E, about 25 to about 69 weight percent trans-1,2-dichloroethylene, and about 30 to about 69 weight percent C₄F₉OCH₃; about 1 to about 50 weight percent F3i4E, about 30 to about 98 weight percent trans-1,2-dichloroethylene, and about 1 to about 60 weight percent C₄F₉OC₂H₅; and about 1 to about 70 weight percent F44E, about 1 to about 60 weight percent trans-1,2-dichloroethylene, and about 29 to about 98 weight percent C₄F₉O C₂H₅.
 13. An azeotropic or azeotrope-like composition comprising an azeotropic or azeotrope-like composition selected from the group consisting of: 85.1 weight percent F14E and 14.9 weight percent methanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 59.1° C.; 87.1 weight percent F14E and 12.9 weight percent isopropanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 66.9° C.; 87.9 weight percent F14E and 12.1 weight percent ethanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 65.2° C.; 44.3 weight percent F14E and 55.7 weight percent trans-1,2-dichloroethylene having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 44.0° C.; 54.4 weight percent F14E and 45.6 weight percent n-propylbromide having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 66.6° C.; 72.1 weight percent F24E and 27.9 weight percent methanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 63.4° C.; 78.1 weight percent F24E and 21.9 weight percent isopropanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 74.1° C.; 25.7 weight percent F24E and 74.3 weight percent n-propylbromide having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 70.2° C.; 85.2 weight percent F24E and 14.8 weight percent perchloroethylene having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 89.9° C.; 65.0 weight percent F24E and 35.0 weight percent trichlorethylene having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 75.9° C.; 95.8 weight percent F22E and 4.2 weight percent methanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 43.7° C.; 98.0 weight percent F22E and 2.0 weight percent isopropanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 47.2° C.; 97.6 weight percent F22E and 2.4 weight percent ethanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 46.6° C.; 71.0 weight percent F22E and 29.0 weight percent trans-1,2-dichlorethylene having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 33.9° C.; 87.0 weight percent F22E and 13.0 weight percent n-propylbromide having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 43.3° C.; 89.8 weight percent F22E and 10.2 weight percent HFC-43-10mee having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 47.9° C.; 29.3 weight percent F22E and 70.7 weight percent HFC-365mfc having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 39.2° C.; 95.5 weight percent F13iE and 4.5 weight percent methanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 44.4° C.; 97.8 weight percent F13iE and 2.2 weight percent isopropanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 48.0° C.; 70.2 weight percent F13iE and 29.8 weight percent trans-1,2-dichlorethylene having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 34.4° C.; 86.4 weight percent F13iE and 13.6 weight percent n-propylbromide having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 44.0° C.; 95.3 weight percent F13iE and 4.7 weight percent HFC-43-10mee having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 48.8° C.; 24.6 weight percent F13iE and 75.4 weight percent HFC-365mfc having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 39.5° C.; 85.0 weight percent F3i3iE and 15.0 weight percent methanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 59.8° C.; 89.2 weight percent F3i3iE and 10.8 weight percent isopropanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 70.0° C.; 89.0 weight percent F3i3iE and 11.0 weight percent ethanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 67.8° C.; 44.1 weight percent F3i3iE and 55.9 weight percent trans-1,2-dichlorethylene having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 44.5° C.; 22.8 weight percent F3i3iE and 77.2 weight percent C₄F₉OC₂H₅ having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 75.7° C.; 67.4 weight percent F3i3iE and 32.6 weight percent n-propylbromide having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 61.3° C.; 94.4 weight percent F13E and 5.6 weight percent methanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 47.3° C.; 96.9 weight percent F13E and 3.1 weight percent isopropanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 51.9° C.; 96.5 weight percent F13E and 3.5 weight percent ethanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 51.1° C.; 66.3 weight percent F13E and 33.7 weight percent trans-1,2-dichloroethylene having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 36.3° C.; 83.7 weight percent F13E and 16.3 weight percent n-propylbromide having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 47.1° C.; 59.5 weight percent F13E and 40.5 weight percent HFC-43-10mee having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 52.3° C.; 7.6 weight percent F3i4E and 92.4 weight percent trans-1,2-dichloroethylene having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 47.6° C.; 42.8 weight percent F3i4E and 57.2 weight percent methanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 65.4° C.; 57.8 weight percent F3i4E and 42.2 weight percent isopropanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 81.0° C.; 58.7 weight percent F3i4E and 41.3 weight percent ethanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 77.3° C.; 31.9 weight percent F3i4E and 68.1 weight percent n-propylbromide having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 69.6° C.; 8.1 weight percent F44E and 91.9 weight percent n-propylbromide having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 70.9° C.; 34.4 weight percent F14E, 59.0 weight percent trans-1,2-dichloroethyene, and 6.6 weight percent methanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 39.9° C.; 41.9 weight percent F14E, 55.1 weight percent trans-1,2-dichloroethyene, and 3.0 weight percent ethanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 43.2° C.; 10.3 weight percent F24E, 80.3 weight percent trans-1,2-dichloroethyene, and 9.4 weight percent methanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 41.0° C.; 24.8 weight percent F24E, 70.9 weight percent trans-1,2-dichloroethyene, and 4.3 weight percent ethanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 43.0° C.; 67.9 weight percent F22E, 29.7 weight percent trans-1,2-dichloroethyene, and 2.4 weight percent methanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 32.6° C.; 45.4 weight percent F22E, 27.2 weight percent trans-1,2-dichloroethyene, and 27.4 weight percent HFC-365mfc having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 33.0° C.; 66.9 weight percent F13iE, 30.6 weight percent trans-1,2-dichloroethyene, and 2.5 weight percent methanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 33.0° C.; 69.8 weight percent F13iE, 29.8 weight percent trans-1,2-dichloroethyene, and 0.4 weight percent HFC-43-10mee having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 34.4° C.; 41.9 weight percent F13iE, 27.8 weight percent trans-1,2-dichloroethyene, and 30.3 weight percent HFC-365mfc having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 33.3° C.; 32.9 weight percent F3i3iE, 60.2 weight percent trans-1,2-dichloroethyene, and 6.9 weight percent methanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 40.1° C.; 41.1 weight percent F3i3iE, 56.3 weight percent trans-1,2-dichloroethyene, and 2.6 weight percent ethanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 43.8° C.; 62.2 weight percent F13E, 34.7 weight percent trans-1,2-dichloroethyene, and 3.1 weight percent methanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 34.5° C.; 48.0 weight percent F13E, 33.2 weight percent trans-1,2-dichloroethyene, and 18.8 weight percent HFC-43-10mee having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 36.1° C.; 23.1 weight percent F13E, 30.3 weight percent trans-1,2-dichloroethyene, and 46.6 weight percent HFC-365mfc having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 34.4° C.;
 14. A composition comprising the azeotrope-like composition of claim 12 and an aerosol propellant.
 15. The composition of claim 14, wherein the aerosol propellant is selected from the group consisting of air, nitrogen, carbon dioxide, difluoromethane, trifluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, heptafluoropropane, and pentafluoropropane.
 16. A composition comprising the azeotropic composition of claim 13 and an aerosol propellant.
 17. The composition of claim 16, wherein the aerosol propellant is selected from the group consisting of air, nitrogen, carbon dioxide, difluoromethane, trifluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, heptafluoropropane, and pentafluoropropane.
 18. A process for cleaning, comprising: a. contacting a surface comprising a residue with the composition of claim 12 and b. recovering the surface from the composition.
 19. The process of claim 18 wherein said residue comprises an oil.
 20. The process of claim 18 wherein said residue comprises a rosin flux.
 21. The process of claim 18 wherein said surface is an integrated circuit device.
 22. A process for cleaning, comprising: a. contacting a surface comprising a residue with the composition of claim 13 and b. recovering the surface from the composition.
 23. The process of claim 22 wherein said residue comprises an oil.
 24. The process of claim 22 wherein said residue comprises a rosin flux.
 25. The process of claim 22 wherein said surface is an integrated circuit device. 